EP1264852B1 - Procédé pour la préparation de résines de polyester - Google Patents

Procédé pour la préparation de résines de polyester Download PDF

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Publication number
EP1264852B1
EP1264852B1 EP02077113A EP02077113A EP1264852B1 EP 1264852 B1 EP1264852 B1 EP 1264852B1 EP 02077113 A EP02077113 A EP 02077113A EP 02077113 A EP02077113 A EP 02077113A EP 1264852 B1 EP1264852 B1 EP 1264852B1
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EP
European Patent Office
Prior art keywords
pet
preparation
process according
weight
polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02077113A
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German (de)
English (en)
Other versions
EP1264852A3 (fr
EP1264852A2 (fr
Inventor
Socrate Contessa
Maria Bisbiglia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGP SpA
Original Assignee
Montefibre SpA
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Publication date
Application filed by Montefibre SpA filed Critical Montefibre SpA
Publication of EP1264852A2 publication Critical patent/EP1264852A2/fr
Publication of EP1264852A3 publication Critical patent/EP1264852A3/fr
Application granted granted Critical
Publication of EP1264852B1 publication Critical patent/EP1264852B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids

Definitions

  • the present invention relates to a process for the preparation of polyester resins.
  • the present invention relates to a process for the preparation of polyethyleneterephthalate using titanium oxide as synthesis catalyst.
  • Catalysts based on titanium dioxide powders having a particular microcrystalline structure have been commercially proposed by the company Acordis and Satchleben, with the aim of eliminating the drawbacks created by the yellow colouring of the PET produced when it is synthesized in the presence of titanium.
  • the results, however, as demonstrated below, are not particularly valid even in the presence of stabilizers such as phosphoric acid or organic phosphates, for example trimethylphosphate.
  • US-A-4,254,018 discloses dimethylterephthalate and ethylene glycol transesterification in the presence of Mn(OAc) 2 to BHET and subsequent polymerization using TiO 2 and triethylphosphonoacetate (PEE).
  • the document "White polyester films” from Chemical Abstracts Service STN database accession n.130:312848 XP002222713 & JP 11 116716 A discloses composition comprising PET, TiO 2 and triethylphosphonoacetate.
  • WO02/068497 discloses a catalyst comprising a titanium compound and a phosphorous compound. Cobalt, antimony, manganese and zinc compounds can be included in the catalytically active composition. The catalyst is used for producing polyesters.
  • the Applicant has now found a method for obtaining PET with improved or comparable characteristics, with respect to both the colour and physico-chemical and processability properties, with standard PET using commercial titanium dioxide as polymerization catalyst, also reducing the concentration of antimonium in the catalytic formulation, to zero.
  • the object of the present invention therefore relates to a process for the preparation of polyethyleneterephtha-late which comprises polymerizing the reagents in the presence of a catalytic system consisting of 0-80% by weight of antimonium and 20-100% by weight of commercial titanium dioxide having a microcrystalline structure and a stabilizer selected from trimethylphosphonoacetate, triethylphosphonoacetate and tributylphosphonoacetate.
  • the PET is synthesized in two steps.
  • dimethylterephthalate and ethylene glycol are transesterified to (2-hydroxyethyl)terephthalate (BHET) operating at a temperature ranging from 160 to 200°C and in the presence of one or more transesterification catalysts selected from organic salts, for example magnesium, cobalt, manganese, zinc and cadmium acetates.
  • BHET (2-hydroxyethyl)terephthalate
  • organic salts for example magnesium, cobalt, manganese, zinc and cadmium acetates.
  • the esterification reaction for producing BHET is effected under slight pressure and a temperature of some tens of degrees, one or two, higher than the reaction with dimethylterephthalate generally without using any catalyst.
  • the BHET is then polymerized in the presence of the stabilizers having formula (I) and the catalytic system object of the present invention at a temperature ranging from 260 to 290°C at pressures lower than 15 Pa.
  • the titanium dioxide catalyst is present in the polymerization mixture in a concentration ranging from 50 to 150 ppm, calculated with respect to the PET produced, whereas the antimonium, expressed as oxide, can be present up to 200 ppm.
  • Titanium dioxide is present on the market under the trade-name of C94, of the company Acordis, or HOMBIFAST PC, of the company Satchleben. This material has a microcrystalline structure which makes it perfectly soluble in the end-polymer.
  • the PET has an intrinsic viscosity, measured from solutions in o-chlorophenol at 35°C in concentrations of 0.6 g per 50 ml, by means of an automatic Shotte-Gerate viscosimeter, ranging from 0.4 to 1.5 dl/g.
  • the polymers thus obtained have characteristics like standard PET and can be subjected to classical extrusion processes for obtaining fibres in the form of both continuous and staple filaments, optionally dyeable, or in the preparation of end-products, films or containers, also for food products.
  • the excess ethanediol is then distilled and when the reaction mass reaches 260°C, the pressure is gradually reduced to 1 mbar, after which the temperature is further increased to 295°C and the mass is left to react under these conditions allowing the reaction ethanediol to be removed.
  • the reaction product is extruded and granulated producing a polymer having an intrinsic viscosity equal to 0.635 and a yellow index, measured with the CieLab system, equal to 8.
  • the total synthesis time evaluated at the beginning of the reaction phase under vacuum until the end of the polycondensation was 81 minutes.
  • PET The synthesis of PET is carried out under the same experimental conditions as Example 1, except for the final temperature which is brought from 295°C to 285°C and for the substitution of the polycondensation catalyst Sb with 0.4 g (equal to 50 ppm with respect to the PET) of TiO 2 available on the market as C94 powder of Acordis.
  • the process stabilizers is still phosphoric acid.
  • the extruded and granulated polymer has an intrinsic viscosity of 0.63 dl/g and a yellow index of 24.
  • the polycondensation proves to be 104 minutes.
  • PET The synthesis of PET is carried out under the same experimental conditions as Example 2, with the substitution of phosphoric acid with an equal quantity of P (14.83 mmoles) added in the form of trimethylphosphate.
  • the extruded and granulated polymer has an intrinsic viscosity of 0.627 dl/g and a yellow index of 19.
  • the polycondensation proves to be 102 minutes.
  • PET The synthesis of PET is carried out under the same experimental conditions as Example 2, with the substitution of phosphoric acid with an equal quantity of P (14.83 mmoles) added in the form of triethylphosphonoacetate.
  • the extruded and granulated polymer has an intrinsic viscosity of 0.622 dl/g and a yellow index of 15.
  • the polycondensation proves to be 89 minutes.
  • PET The synthesis of PET is carried out under the same experimental conditions as Example 2, but using as catalyst TiO 2 in powder form sold under the trade-name of HOMBIFAST PC of Satchleben (the stabilizers is phosphoric acid).
  • the extruded and granulated polymer has an intrinsic viscosity of 0.648 dl/g and a yellow index of 23.
  • the polycondensation proves to be 82 minutes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (6)

  1. Procédé de préparation de poly(éthylène téréphtalate) PET, qui comporte le fait de faire polymériser les réactifs en présence d'un système catalytique constitué de 0 à 80 % en poids d'antimoine et de 20 à 100 % en poids de dioxyde de titane du commerce présentant une structure microcristalline et un stabilisant choisi parmi le phosphonoacétate de triméthyle, le phosphonoacétate de triéthyle et le phosphonoacétate de tributyle.
  2. Procédé conforme à la revendication 1, dans lequel la préparation du PET comporte, avant la polymérisation, une première étape de transestérification dans laquelle on effectue la transestérification de téréphtalate de diméthyle, avec de l'éthylèneglycol, en téréphtalate de 2-hydroxyéthyle, en opérant à une température de 160 à 200 °C et en présence d'un ou plusieurs catalyseurs de transestérification choisis parmi les sels organiques de magnésium, de cobalt, de manganèse, de zinc ou de cadmium.
  3. Procédé conforme à la revendication 1, dans lequel la préparation du PET comporte, avant la polymérisation, une première étape de réaction dans laquelle on effectue avec de l'éthylèneglycol l'estérification d'acide téréphtalique en téréphtalate de 2-hydroxyéthyle, en opérant à une température supérieure d'une ou deux dizaines de degrés à celle indiquée pour la réaction partant de téréphtalate de diméthyle, et en l'absence de catalyseur.
  4. Procédé conforme à l'une des revendications précédentes, dans lequel l'étape de polymérisation est effectuée à une température de 260 à 290 °C et sous une pression inférieure à 15 Pa.
  5. Procédé conforme à l'une des revendications précédentes, dans lequel le catalyseur dioxyde de titane se trouve dans le mélange de polymérisation en une concentration qui, calculée par rapport au PET produit, vaut de 50 à 150 ppm, alors que l'antimoine s'y trouve en une concentration qui, calculée pour l'oxyde, vaut au plus 200 ppm.
  6. Procédé conforme à l'une des revendications précédentes, dans lequel le stabilisant est ajouté au mélange de polymérisation en une quantité représentant de 0,01 à 0,5 % du poids total du mélange.
EP02077113A 2001-06-07 2002-05-29 Procédé pour la préparation de résines de polyester Expired - Lifetime EP1264852B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2001MI001206A ITMI20011206A1 (it) 2001-06-07 2001-06-07 Procedimento per la preparazione di resine poliesteri
ITMI20011206 2001-06-07

Publications (3)

Publication Number Publication Date
EP1264852A2 EP1264852A2 (fr) 2002-12-11
EP1264852A3 EP1264852A3 (fr) 2003-02-12
EP1264852B1 true EP1264852B1 (fr) 2004-07-28

Family

ID=11447829

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02077113A Expired - Lifetime EP1264852B1 (fr) 2001-06-07 2002-05-29 Procédé pour la préparation de résines de polyester

Country Status (7)

Country Link
EP (1) EP1264852B1 (fr)
AT (1) ATE272087T1 (fr)
DE (1) DE60200816T2 (fr)
ES (1) ES2225725T3 (fr)
IT (1) ITMI20011206A1 (fr)
PT (1) PT1264852E (fr)
TR (1) TR200402679T4 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1535946A1 (fr) * 2003-11-28 2005-06-01 Futura Polymers Procédé pour la fabrication de polyéthylène-térephthalate
CN108690184A (zh) * 2017-04-07 2018-10-23 浙江佳人新材料有限公司 一种用于化学循环法生产大有光切片的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2708790C2 (de) * 1977-03-01 1982-02-25 Akzo Gmbh, 5600 Wuppertal Lineare Homo- oder Copolyester, Verfahren zur Herstellung der Polyester und ihre Verwendung
JPH11116716A (ja) * 1997-10-21 1999-04-27 Toray Ind Inc 白色ポリエステルフイルム
US6489433B2 (en) * 2001-02-23 2002-12-03 E. I. Du Pont De Nemours And Company Metal-containing composition and process therewith

Also Published As

Publication number Publication date
ES2225725T3 (es) 2005-03-16
EP1264852A3 (fr) 2003-02-12
EP1264852A2 (fr) 2002-12-11
DE60200816D1 (de) 2004-09-02
ITMI20011206A1 (it) 2002-12-07
ITMI20011206A0 (it) 2001-06-07
TR200402679T4 (tr) 2004-11-22
ATE272087T1 (de) 2004-08-15
DE60200816T2 (de) 2005-09-22
PT1264852E (pt) 2004-12-31

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